JP2003181406A - Method and apparatus for hydrothermal reaction - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent the discharge of an undecomposed material or an reaction intermediate by controlling a hydrothermal reaction to surely decompose an organic material. <P>SOLUTION: The hydrothermal reaction is carried out using an apparatus having a reactor 12 in which the organic material to be treated and an oxidizing agent are supplied and hydrothermally reacted with each other at the simpler critical state or the sub critical state, a measurement instrument 20 for measuring CO quantity in a treating fluid and a controller (controller 21) for controlling the hydrothermal reaction based on the measured CO quantity. Each process is controlled by sending control signals S1-S4 from the controller. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrothermal reaction method in which an organic material to be treated is hydrothermally reacted in the presence of an oxidant in a supercritical or subcritical state of water, and particularly by controlling the reaction. The present invention relates to a hydrothermal reaction method capable of reliably decomposing an object to be treated.

[0002]

2. Description of the Related Art Conventionally, in the decomposition of waste, the generation of energy, the production of chemical substances, etc., a method of utilizing a hydrothermal reaction to oxidize or hydrolyze an object to be treated has been used. Particularly in recent years, attention has been focused on a hydrothermal reaction method in which a substance to be treated is reacted with water containing an oxidant in a supercritical state of water or a subcritical state close to it, and organic substances in the substance to be treated can be almost decomposed in a short time. Has been done. In this method, the organic matter in the material to be treated becomes a high-temperature and high-pressure reaction product composed of water and carbon dioxide by an oxidation reaction including combustion. Energy of the reaction product is recovered, or the reaction product is cooled and decompressed to be separated into a gas component and a liquid component.

When a hydrothermal reaction is carried out in the supercritical or subcritical state of water, it is necessary to control the reaction. For example, the heat of reaction is generated by the oxidation reaction, and the temperature inside the device such as the reactor rises. Therefore, prevent the temperature in the equipment such as the reactor from exceeding the allowable temperature of the equipment material by diluting the concentration of the reactants in the reactor with water or cooling the interior of the reactor by adding water. Controlled. On the other hand, if the amount of heat in the reactor is too low, it is necessary to obtain the reaction temperature necessary for the decomposition of organic matter, so heat from the outside or auxiliary fuel should be added to raise the temperature in the reactor. There is. Known auxiliary fuels are kerosene, isopropyl alcohol, methanol and the like.

If the decomposition of the material to be processed in such a hydrothermal reaction is incomplete, the processing fluid containing undecomposed organic matter and reaction intermediates is discharged, causing environmental pollution. Therefore, it is also necessary to control the reaction to ensure the decomposition. The cause of the incomplete decomposition is, for example, a lack of an oxidizing agent. Specifically, there are cases where the oxidant becomes insufficient with respect to the object to be processed or the auxiliary fuel supplied, or when the oxidant is insufficient when the type of the object to be processed is switched. Even if the oxidant required for the object to be treated is calculated in advance and the oxidant in excess of the predicted required amount is added, the oxidant may be insufficient. this is,
Since the content of the object to be supplied is not uniform, the addition of a fixed amount of the oxidizing agent continuously causes an excess or insufficient amount of the oxidizing agent to oxidize the object to be treated. . On the other hand, it is possible to supply a large amount of the oxidizing agent, but if the oxidizing agent is used in an excessive amount, it will be costly and the reactor will need to be upsized. Also,
Another cause of insufficient decomposition reaction is low reaction temperature. However, in order to carry out the reaction at a high temperature, a reactor having excellent heat resistance is required, which increases equipment cost.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to propose a hydrothermal reaction method and apparatus which can surely decompose an object to be treated without waste and at low cost.

[0006]

The present invention provides the following hydrothermal reaction method and hydrothermal reaction apparatus. (1) A hydrothermal reaction step in which an organic substance to be treated and an oxidant are supplied into a reactor and a hydrothermal reaction is performed in a supercritical or subcritical state of water, and measurement for measuring the amount of CO in a treated fluid A hydrothermal reaction method comprising a step and a control step of controlling the hydrothermal reaction so that the measured CO amount becomes a predetermined value or less. (2) The method according to (1) above, wherein when the amount of CO in the treatment fluid exceeds a predetermined value, the control step is performed by at least one control means of the following (a) to (c). (A) Increase the supply of oxidant. (B) The supply amount of the object to be processed is reduced. (C) Raise the reaction temperature. (3) A reactor for supplying an organic object to be treated and an oxidant to cause a hydrothermal reaction in a supercritical or subcritical state of water, a measuring device for measuring the amount of CO in the treated fluid, and CO
A hydrothermal reaction device comprising: a control device that controls the hydrothermal reaction so that the amount thereof becomes a predetermined value or less. (4) Since the control device controls the hydrothermal reaction when the amount of CO in the treated fluid exceeds a predetermined value, the following (a)-
The hydrothermal reaction device according to (3) above, which has at least one control means of (c). (A) Increase the supply of oxidant. (B) The supply amount of the object to be processed is reduced. (C) Raise the temperature in the reactor.

The object to be treated in the present invention is an organic object to be treated and contains an organic substance which can be oxidatively decomposed by a hydrothermal reaction. Specific examples include waste liquid, waste, waste solvent, sludge, human waste, sewage, bacteria, plastic waste, membrane, adsorption resin, ion exchange resin, activated carbon and the like. The object to be treated may contain an inorganic substance in addition to the organic substance.

In the hydrothermal reaction step of the present invention, a hydrothermal reaction is carried out by supplying an object to be treated, an oxidant, an auxiliary fuel, water and the like as the object to be reacted from the supply port into the reactor. Specifically, the object to be treated is decomposed by hydrothermal reaction in the supercritical or subcritical state of water in the presence of an oxidizing agent. Decomposition is performed by, for example, oxidative decomposition, hydrolysis, etc. of the object to be treated. The supercritical state is a state of 374 ° C. or higher and 22 MPa or higher. The subcritical state is, for example, 374 ° C. or higher, 2.5 MPa or higher 2
A state of less than 2 MPa, less than 374 ° C., 22 MPa or more, or a temperature of 374 ° C. or less, less than 22 MPa is a high temperature / high pressure state close to the critical point.

The oxidizing agent is not particularly limited, but examples thereof include air, oxygen-enriched air, oxygen, liquid oxygen, hydrogen peroxide solution, and nitrates. When the amount of heat of the object to be treated is insufficient in the hydrothermal reaction, the auxiliary fuel is supplied to the reactor to carry out the reaction. Examples of auxiliary fuels include kerosene, kerosene, isopropyl alcohol, methanol and the like. The auxiliary fuel does not have to be a pure substance, and may be, for example, a waste solvent containing other organic substances, inorganic substances, water and the like.

The reactor for carrying out the hydrothermal reaction may take any form as long as the reaction can be carried out safely and stably. For example, a tube type reactor, a vessel type reactor, a cylinder type reactor or the like, JP-A-11-15618.
Vertical cylindrical reactor as shown in Japanese Patent No.
A tubular reactor such as that disclosed in Japanese Patent No. 036077 may be used. The reactor is made of a heat resistant and pressure resistant material so that the hydrothermal reaction can be performed in a supercritical or subcritical state. For example, a reactor formed of a corrosion resistant material such as Hastelloy, Inconel, or stainless is preferable. An external heating means can be provided outside the reactor in case the reaction heat alone does not reach a supercritical or subcritical state.

[0011] Such a reactor is preferably connected with a reactant supply passage to which a material supply passage, an oxidant supply passage, an auxiliary fuel supply passage, and a water supply passage are connected. Alternatively, the mixture supply passage and the oxidant supply passage extending from the mixing portion where the material to be treated, the auxiliary fuel, and water are mixed in advance may be connected to the reactant supply passage, and the reactant supply passage may be connected to the reactor. . It is preferable that the reactant supply paths are configured to mix the respective reactants.

At the start of the hydrothermal reaction, the reactor is usually preheated to a temperature near a predetermined reaction temperature, and the substances to be treated such as the substances to be fed into the reactor are also preheated. Preheating of the substance to be reacted can be carried out by providing a heating device in the reactor, the substance supply passage for the treatment object, the oxidant supply passage, or the like. Further, usually, water or an oxidant is supplied to the reactor, and the pressure is adjusted to a predetermined pressure by a pressure adjusting valve which is usually provided. Predetermined temperature,
After the pressure is adjusted, the reactant is supplied to start the hydrothermal reaction.

As a preferable method of supplying the reactant, first, the auxiliary fuel and water are supplied into the reactor to start the hydrothermal reaction. Then, when the hydrothermal reaction continues in the reactor and becomes stable, the addition of the object to be treated is started, the supply amount of the object to be treated is gradually increased, the supply amount of the auxiliary fuel is decreased, and the final Specifically, the supply of auxiliary fuel is stopped, and only the object to be processed is processed by hydrothermal reaction. As described above, when the supplied reaction target is switched from the auxiliary fuel to the processing target and supplied, the hydrothermal reaction can be efficiently and reliably performed. Furthermore, it is preferable to separately supply the air and the portion including the object to be treated, the auxiliary fuel, and the water. To supply separately, for example, a double tube nozzle can be used. In addition, when the reaction target is a liquid, a high-pressure pump or the like can be used, and when the reaction target is a gas, a pneumatic compressor such as an air compressor or a booster can be used.

The reaction temperature and pressure in the hydrothermal reaction are
The temperature and pressure are set so that water becomes supercritical or subcritical, but it is preferable to set the reaction temperature to a predetermined temperature in order to stably and surely decompose the object to be treated. For example, for the decomposition of general organic matter, 374 to 800
C., preferably 450 to 800.degree. C., can be decomposed into carbon dioxide gas and water. 374-800 when containing ammonia nitrogen or organic nitrogen
By controlling the temperature to be ℃, preferably 550 to 800 ℃, it is possible to decompose into nitrogen gas.

Since the reaction temperature fluctuates due to the fluctuation of the total calorific value of the reaction target, it is preferable to control the temperature while monitoring the reaction temperature of the hydrothermal reaction. When the material to be treated contains sufficient water, it is not necessary to supply water, but when the amount of water is insufficient or the amount of heat is too large and the temperature becomes too high, dilution water can be supplied. It should be noted that the reaction pressure in the hydrothermal reaction does not affect the physical properties of the treated material as much as the reaction temperature does, so it need not be particularly considered, but it is desirable to maintain a constant level for stable control.

When the hydrothermal reaction is carried out in the reactor in the supercritical or subcritical state of water as described above, the organic matter of the object to be treated is oxidized by the oxidizing agent and finally decomposed into water and carbon dioxide. It Alternatively, it is hydrolyzed to have a low molecular weight, and the inorganic substance is separated in a solid or molten state. After the hydrothermal reaction, the treatment fluid (reaction product) is discharged from the outlet, cooled and decompressed, and separated into a gas component, a liquid component, and a solid substance.

When the amount of CO (carbon monoxide) in the discharged processing fluid is high, the decomposition of organic substances in the material to be processed is incomplete. Therefore, in the hydrothermal reaction method of the present invention, the amount of CO in the treated fluid is measured by a measuring device in the measuring step to confirm whether or not the decomposition of the organic matter is reliably performed in the reactor, and the measured value is measured. The hydrothermal reaction is controlled so that the CO amount becomes equal to or less than a predetermined value.

The measuring device used in the measuring step is not particularly limited as long as it measures the CO amount in the treatment fluid, but a device measuring the CO amount as the CO concentration is preferable.
In this case, the CO concentration in the treatment fluid immediately after the reaction may be directly measured, or the CO concentration in the treatment gas separated from the treatment fluid may be measured. Specifically, for example, a commercially available infrared type gas detection device can be provided in the gas discharge passage to measure the amount of CO in the treatment fluid. The measurement may be performed continuously or intermittently at predetermined time intervals. When continuously performed, the control based on the amount of CO can be performed without delay, and the organic matter can be decomposed more reliably. The measurement value measured in this way is
It is sent to the control process.

In the control step, the hydrothermal reaction is controlled by the controller according to the measured CO amount. When the amount of CO is high, the decomposition is not completely performed. Therefore, measures are taken to accelerate the decomposition, and the hydrothermal reaction is controlled so that the amount of CO becomes a predetermined value or less. By controlling the hydrothermal reaction in this manner, it becomes possible to surely decompose the organic matter in the hydrothermal reaction. When the amount of CO is low, it can be estimated that the decomposition is almost completely performed. Therefore, no particular control may be performed, or the measures taken to accelerate the decomposition may be suppressed. A computer can be used as the control device and programmed to perform the above control.

The control means in the control process is not particularly limited. Specifically, when the amount of CO exceeds a predetermined value, it is preferable to take at least one means selected from the group consisting of the following (a) to (c) in the hydrothermal step. (A) Increase the supply of oxidant. (B) The supply amount of the object to be processed is reduced. (C) Raise the reaction temperature. In addition, when reducing the above-mentioned (b) supply amount of a to-be-processed object, it is preferable to adjust so that the supply amount of water may be reduced according to the decrease in the supply amount of a to-be-processed object. The means for raising the reaction temperature (c) is not particularly limited. For example, the reaction temperature can be raised by increasing the supply amount of the oxidant, decreasing the supply amount of water, or supplying a larger amount of auxiliary fuel.

In such a control process, a standard value is set for the CO amount of exhaust gas, and the measured value of CO concentration exceeds the standard.
Alternatively, it is preferable that a control means for controlling the hydrothermal reaction is activated so that the CO amount becomes equal to or less than the upper limit of the reference value when the value approaches the reference value. Then, as a result of controlling the hydrothermal reaction in the control step, when the CO amount becomes lower than the reference value, it is preferable that the control means operates so that the CO amount becomes equal to or higher than the lower limit value of the reference value. This makes it possible to avoid the excessive use and excessive heating of the oxidant by operating the control means only when there is a sign that the organic matter is not decomposed. Therefore, using existing equipment,
That is, it is possible to reliably decompose organic substances at low cost without the need to newly introduce large equipment or equipment having high heat resistance.

In the present invention, the control means C starts control.
As the O amount, for example, the upper limit of the reference value of the CO concentration in the processing gas separated from the processing fluid can be set to 5 ppm. If the concentration is less than the CO concentration, it is assumed that the decomposition of organic substances in the reactor is almost certainly performed. On the other hand, when the concentration is higher than this CO concentration, the decomposition by the hydrothermal reaction is not completely performed, and there is a high possibility that undecomposed organic matters and reaction intermediates will be discharged. Control is needed. As the lower limit of the reference value, for example, 0.5 ppm can be set as the CO concentration. If it is lower than this value, the oxidizing agent may be in excess, so that it can be controlled to eliminate this. Specifically, the reverse control operations of (a), (b), and (c) include operations such as decreasing the supply amount of the oxidant, increasing the supply amount of the object to be treated, and lowering the reaction temperature. is there.

When the reference value of the CO concentration for starting the control means is not provided as described above, the control means may be started according to the rate of change of the CO concentration in the treatment liquid. For example, the following methods can be given as specific control methods. When the CO concentration increases by 20% as compared with the CO concentration immediately after the start of the hydrothermal reaction, it is preferable to increase the amount of the oxidizing agent by 15 to 30%. When the CO concentration increases by 20% compared to the CO concentration immediately after the start of the hydrothermal reaction, the treated object is
-30% reduction is preferred. When the CO concentration increases by 20% as compared with the CO concentration immediately after the start of the hydrothermal reaction, it is preferable to raise the reaction temperature by about 10 to 50 ° C.

As described above, the hydrothermal reaction apparatus of the present invention used in the hydrothermal reaction method supplies an organic material to be treated and an oxidant to cause a hydrothermal reaction in a supercritical or subcritical state of water. It has a reactor, a measuring device that measures the amount of CO in the treated fluid, and a controller that controls the hydrothermal reaction based on the measured amount of CO.

[0025]

In the hydrothermal reaction method of the present invention, the amount of CO in the treated fluid is measured and the reaction is controlled according to the amount of CO, so that the organic substances can be decomposed reliably without waste. . Moreover, since the auxiliary fuel can be supplied as needed, the reaction can be performed at low cost without excessively supplying the auxiliary fuel. The hydrothermal reaction device of the present invention has a control device that measures the amount of CO in the treatment fluid and controls the reaction according to the amount of CO. Since the device does not need high heat resistance and does not need to be particularly large, the device can surely decompose organic substances at low cost.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to FIG.
The hydrothermal reaction method of the embodiment will be described using a flow chart, but the present invention is not limited to this. In FIG.
1 is a reaction system, 2 is an oxidant supply source, 3 is an air compressor, 5 is a water tank, 8 is an object tank, 10 is an auxiliary fuel tank, 1
2 is a reactor, 14 is a heat exchanger, 15 is a gas-liquid separator, 2
Reference numeral 0 is a gas analyzer, and 21 is a control circuit.

In the reaction system 1, air is used as the oxidant, and the oxidant supply source 2 communicates with the air compressor 3. The oxidant supply passage 4 extending from the air compressor 3 has an external heat source H1 and the injector 1 of the reactor 12
I have contacted 2a. A water supply path 6 extending from the water tank 5 has a pump P1 and is connected to the reactant supply path 7. An object supply path 9 extending from the object tank 8 has a pump P2 and communicates with the object supply path 7. The auxiliary fuel supply passage 11 extending from the auxiliary fuel tank 10 has a pump P3 and is connected to the reactant supply passage 7. The reactant supply path 7 communicates with the injection device 12 a of the reactor 12. The discharge passage 13 extending from the reactor has a heat exchanger 14, and the gas-liquid separator 1
I am contacting 5. A gas discharge passage 17 and a liquid discharge passage 18 extend from the gas-liquid separator 15. A gas analyzer 20 is provided in the gas discharge path 17, the gas analyzer 20 measures the CO concentration in the processing gas, and the measurement signal D1 indicates the control device 21.
Connected to be input to. The reactor 12 is provided with a temperature sensor 12b and is connected so that the temperature signal D2 is input to the control device. The control device 21 is connected so that control signals S1, S2, S3 and S4 are transmitted to the air compressor 3 and the pumps P1, P2 and P3, respectively.

In the reaction system 1 shown in FIG. 1, the reactor 12 has an external heating source and a pressure control valve, and has a predetermined temperature inside the reactor.
After adjusting the pressure, the supply of the reactant is started. Air as the oxidant is supplied from the oxidant supply source 2 to the air compressor 3
And is heated by the external heat source H1 and sent to the reactor 12. Further, the auxiliary fuel is sent from the auxiliary fuel tank 10 to the reactor 12 via the auxiliary fuel supply passage 11 having the pump P3. Here, the air and the auxiliary fuel are not mixed but sent separately. Then, the auxiliary fuel is mixed with air in the injection device 12 a of the reactor 12 and supplied to the reactor 12. At this time,
It is preferable to use a double tube nozzle as the injection device 12a.

The hydrothermal reaction is started in the reactor 12 by using the air and the auxiliary fuel thus supplied. When the stable supercritical or subcritical state continues, the supply of the object to be processed is started. The material to be processed in the material to be processed tank 8 is supplied from the material to be processed supply path 9 to the reactant to be supplied path 7 by the pump P2. In addition, if necessary, water is pumped from the water tank 5 to the pump P.
1 is sent to the water supply path 6 and further to the reactant supply path 7. In the reactant supply path 7, the water and the object to be treated are mixed with the auxiliary fuel, and the injection device 1 of the reactor 12 is further added.
At 2a, the air is mixed and fed into the reactor 12. In the reactor 12, the organic matter to be treated is oxidized by the oxidant and finally decomposed into water and carbon dioxide.
Here, when the oxidative decomposition is not completely performed due to changes in the organic matter concentration of the object to be treated, the supply amount, etc., CO comes to be discharged into the treatment fluid.

The reaction product is discharged from the discharge port as a processing fluid, cooled through the heat exchanger 14 provided in the discharge path 13, and sent to the gas-liquid separation device 15. In the gas-liquid separator 15, the treated water containing solid matter and the treated gas are separated. The treated water is decompressed by the valve V2 and discharged from the liquid discharge passage 18. On the other hand, the processing gas such as CO ₂ and N ₂ is decompressed by the valve V1 and sent to the gas exhaust passage 17. Further, the processing gas is sent to the gas analyzer 20, and the CO concentration in the processing gas is measured.

The measured CO concentration measurement signal D1 is input to the control device 21. When the CO concentration exceeds a predetermined concentration, the control device 21 sends at least one or more control signals S1, S2, S3, S4 for controlling the hydrothermal reaction to each process. Specifically, the control device 21
Then, a computer or the like constantly checks whether or not the CO concentration exceeds a predetermined concentration, and when the CO concentration exceeds the predetermined concentration, a process of transmitting a control signal to each process is performed. Which control signal is transmitted by the controller 21 depends on the CO
It can be set as appropriate depending on the concentration, the reaction temperature, the reaction pressure, the type of the object to be treated and the like. Further, these control steps can be set to perform a plurality of steps at the same time.

In the control step, the air compressor 3 can be controlled by the control signal S1 to increase the supply amount of air as the oxidant. Alternatively, the supply amount of water can be reduced by controlling the pump P1 for sending out water by the control signal S2. Further, the control signal S3 can control the pump P2 for sending out the object to be processed to reduce the supply amount of the object to be processed. At this time,
It is preferable to control the pump P1 for sending out water by the control signal S2 in accordance with the decrease in the supply amount of the object to be processed so that the supply amount of water is also decreased. Further, the control signal S4 can control the pump P3 for feeding the auxiliary fuel, increase the supply of the auxiliary fuel, and raise the temperature in the reactor 12. In these cases, the temperature inside the reactor 12 is measured by the temperature sensor 12b provided in the reactor 12, and the measured temperature signal is sent to the control device 21. Then, it is possible to control transmission and stop of the control signals S1 to S4 so as to increase the temperature. By continuously performing such control during the hydrothermal reaction process and always keeping the CO concentration in the treated gas at a predetermined concentration or less, the decomposition of organic substances can be ensured, and undecomposed substances and reaction intermediates are discharged. Can be prevented.

By the above control, when the CO concentration in the processing gas becomes lower than the predetermined concentration, control signals S1 to S4 for stopping the control or returning to the normal operation are sent to each step. Specifically, the supply amount of the oxidant is reduced by the control signal S1. The control signal S3 increases the supply amount of the object to be processed, and the control signal S2 accordingly increases the supply amount of water. The supply amount of the auxiliary fuel is reduced by the control signal S4. By controlling in this way,
The efficiency of the hydrothermal reaction treatment of the object to be treated is not reduced, and the auxiliary fuel used is less likely to be wasted.

In the above embodiment, only the auxiliary fuel and the oxidizing agent are supplied at the start of the reaction, but the object to be treated may be supplied together with the auxiliary fuel and the oxidizing agent to start the reaction. Good. Further, depending on the type of the reaction object, the hydrothermal reaction can be performed without supplying auxiliary fuel or water. When an oxidant other than air is used, the oxidant can be sent from the oxidant supply source to the reactor using a high pressure pump.

[0035]

EXAMPLES Examples of the present invention will be described below. Example 1 A hydrothermal reaction was carried out using a waste liquid of a surfactant (TOC 25000 mg / L) as a liquid to be treated. The reaction system was the same as that shown in FIG. 1, and the inner diameter of the reactor was 9.45.
A stainless steel tube having a length of 300 mm and a length of 300 mm was used. 35% hydrogen peroxide solution is supplied as an oxidant instead of air from an oxidant supply source, preheated to 370 ° C. by an external heat source in the piping section, mixed with the liquid to be treated just before the injection port, and a high-pressure pump is used. Was pressed into the reactor (hydrogen peroxide water: 1.5 mL / m
in, object to be treated: 2.0 mL / min). A ceramic heater and a thermocouple provided inside were used in the reactor so that the temperature of the processing fluid was 650 ° C. The pressure inside the reactor was adjusted to 24 MPa with a pressure regulating valve provided at the outlet of the reactor. After the reaction temperature and pressure in the reactor became stable, the reaction was continued for 1 hour.

In the hydrothermal reaction, the discharged reaction product was treated gas separated by a gas-liquid separator and depressurized. The CO concentration in the treated gas was monitored by an infrared gas detector. When the CO concentration is less than 5 ppm, the hydrogen peroxide supply rate is 1.5 ml / min, and when it is 5 ppm or more,
The high-pressure pump that supplies the oxidizing agent was controlled so that the hydrogen peroxide supply rate was 2.0 ml / min. As a result, TOC in the treatment liquid was 14 mg / L, and the decomposition of organic substances was almost completely performed.

Comparative Example 1 In the same manner as in Example 1, a hydrothermal reaction was carried out using the waste liquid of the surfactant as the liquid to be treated. However, the CO concentration was not measured and controlled, and the supply amount of hydrogen peroxide solution was always kept constant. As a result, the TOC in the treatment liquid was 130 mg / L, and the decomposition of organic substances was not completed completely. The amount of oxidizer is TO
Since more than the equivalent amount to C was added, it is presumed that the liquid to be treated was not uniform in the reactor, and thus the oxidizer was insufficient.

[Brief description of drawings]

FIG. 1 is a flow chart showing a hydrothermal reaction method according to an embodiment of the present invention.

[Explanation of symbols]

1 reaction system 2 Oxidant supply source 3 Air compressor 4 Oxidant supply path H1 external heat source 5 aquarium 6 water supply channel 7 Reactant supply path 8 Processing object tank 9 Processing object supply path 10 Auxiliary fuel tank 11 Auxiliary fuel supply path 12 reactor 12a injection device 12b Temperature sensor 13 discharge path 14 heat exchanger 15 Gas-liquid separation device 17 gas discharge channel 18 Liquid discharge path 20 gas analyzer 21 Control circuit S1, S2, S3, S4 control signals

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) B09B 3/00 304P 304L (71) Applicant 598124412 General Atomics Incorporated United States San Diego General Atomic Co. 3550 (72) Inventor Masaaki Wakita 3-4-7 Nishishinjuku, Shinjuku-ku, Tokyo Within Kurita Industry Co., Ltd. (72) Inventor Kunito Suzuki 1200 Manda, Hiratsuka-shi, Kanagawa Komatsu Ltd. F-term ( Reference) 4D004 AA02 AA06 AA47 BA06 CA39 CB31 DA01 DA02 DA10 4D050 AA12 AA16 AB11 BB00 BB01 BC02 CA01 4D059 AA07 BC02 BC03 EA09 EB09

Claims (4)

[Claims] 1. A hydrothermal reaction step of supplying an organic substance to be treated and an oxidant into a reactor and performing a hydrothermal reaction in a supercritical or subcritical state of water, and measuring the amount of CO in a treated fluid. And a control step of controlling the hydrothermal reaction so that the measured CO amount becomes equal to or less than a predetermined value. 2. The method according to claim 1, wherein when the amount of CO in the treatment fluid exceeds a predetermined value, the control step is performed by at least one control means of the following (a) to (c). (A) Increase the supply of oxidant. (B) The supply amount of the object to be processed is reduced. (C) Raise the reaction temperature. 3. An organic material to be treated and an oxidant are supplied,
Reactor for hydrothermal reaction in supercritical or subcritical state of water, measuring device for measuring CO amount in treated fluid, control for controlling hydrothermal reaction so that measured CO amount is below a predetermined value And a hydrothermal reactor having a device. 4. The control device controls the hydrothermal reaction when the amount of CO in the treatment fluid exceeds a predetermined value.
The hydrothermal reaction device according to claim 3, further comprising at least one control means of (c) to (c). (A) Increase the supply of oxidant. (B) The supply amount of the object to be processed is reduced. (C) Raise the temperature in the reactor.